Esters of 4, 4-bis (hydroxyphenyl)-pentanoic acid



United States Patent 1 2,933,521 ESTERS OF 4,4-BIS(HYDROXYPHENYL)-PENTANOIC ACID Sylvan Owen Greenlee, Racine, Wis, assignor to S. C.

Johnson & Son, Inc., Racine, Wis.

No Drawing. Continuation of application Serial No. 500,695, April 11,1955. This application July 17, 1957, Serial No. 672,356

6 Claims. (Cl. 260-473) This invention relates to new chemical compoundsderived from an alcohol and a novel organic acid. More particularly,this invention relates, to new esters prepared from a long-chainunsaturated alcohol and .an acid which is substituted with polymerizablegroups. This is a continuation of my earlier co-pending application S.N.500,- 695, filed April 11, 1955 now abandoned.

in the formulation of plasticized resin compositions, one of thegreatest problems encountered is the manner of plasticizing andimparting air-drying or heat conversion characteristics while retainingother desired properties. According to conventional practice, the resinis compounded with one or more materials which contribute theplasticizing and/or drying characteristics. Since the resin andplasticizer or drying oil must be completely miscible with one another,certain other properties of the resin are sacrificed. For example, aformulator will choose a very soluble resin because of its miscibilityeven though the product is inferior with respect to toughness, chemicalresistance or flexibility.

important resin plasticizers are the drying oils, which contain theglycerides of unsaturated acids'of 18 to 22 carbon atoms, and vthereduction products of such oils. These oils are highly desirable notonly for plasticizing',

but also for the conversion characteristics which they impart due totheir unsaturation. The present compositions provide a means ofchemically uniting in each molecule one or more plastieizing orconverting groups which may be derived from such drying oils togetherwith a residue capable of being treated to form valuable insoluble,infusible compositions.

Compounds capable of accomplishing the above ends are the esters oflong-chain unsaturated alcohols and an aryl-suhstituted pentanoic acid.Such compositions may be prepared, for example, by reacting 1 mol of aDiphenolic Acid, such as 4,4-bis(hydroxyphenyl)-pentanoic acid, with 1mol of 9,'l0-octadecenol, also known as oleyl alcohol, a reductionproduct of oleic acid.

to be understood that the phenolic nuclei of the 'Diphenolic Acids maybe substituted with any groups which will not interfere with theesterification reactions. For example, the nuclei may be alkylated asdisclosed in Serial No. 489,300 or they may be halogenated. Thelong-chain unsaturated alcohols suitable for use in preparing theestersof this invention include those containing at least about 19 carbonatoms. Illustrative of such alcohols are the'reduction products ofnatural-occurring unsaturated oils, such as china wood oil, dehydratedcastor oil, linseed oil, soya bean oil, corn on, "and cottonseed oil.The fish oils constitute an additionalfim portant source of operableunsaturated alcohols. They contain the glycerides of highly unsaturatedacids and have an iodine value ranging from about to These alcohols areusually prepared by selective 'reduc tion of the corresponding oils orthe simpler esters'of the oil acids. A typical method is the sodiumreduction, whereby the ester group is reduced to a hydroxyl groupwithout saturating the olefin group. Alcohols having a lower molecularweight may also be used, but these con taining less than about 10 carbonatoms contribute little plasticization. The upper limit on the chainlength of operable alcohols is determined only by their availabilitysince any high molecular weight alcohol will impart pl'a's ticizing. Ifair-drying characteristics are considered paramount, it would be betterto choose a lower molecular weight material. Undecenol is an example ofone of the lower unsaturated alcohols contemplated herein. It may beobtained by reducing undecenoic acid, the decomposition product ofcastor oil acids. Similar alcohols m'ay, in some cases, be made bymodification of the naturally occurring oil products. For example,methyl oleate might be oxidized to dihydroxymethyl stearate, a materialwhich on dehydration yields the corresponding methyl octadeca dienoate.the corresponding octadecadienol. v H

The synthetic esters as herein disclosed are conveniently prepared bydirect heating at temperatures of from 1 99 275 C. under couditionswherethe water produced during condensation is continuously removed as it isformed; Since the Diphenolic Acid compounds'are prepared from thelong-chain unsaturated alcohols having boiling points which are inexcess of 190 C., the water may be removed by permitting it tovolatilize during esterification. Removal of the water may also befacilitated by continuous; 1y bubbling through the reaction mixtureduring esterifii cation a stream of inert gas such as carbon dioxide or:

nitrogen. It is also sometimes convenient to facilitate the waterremoval'by carrying out the reaction in a vessel provided with acondenser-attached thereto through a water trap, adding a suficientamount of a volatile water} insoluble solvent to give reflux at theesterification tem-' perature, and continually removing the water byazeotropic distillation permitting the solvent to return to the rcactionmixture after having dropped the water in the water trap.

The new esters of the instant invention each contain within the samemolecule an unsaturated residue of the plasticizing type, together withaf group which is very re'-'- active with certain materials to formcompositions highly sensitive to polymerization to infusible, insolublecoating or molding products. Bis(4-hydroxyphenyl) isopropylidene, alsoknown asbisphenol, is very similar to the dihydrie phenol structurefound in the subject mixed esters. When reacted with either aldehydes orepoxides, this material yields compositions which are almostquantitatively insoluble in drying oils and the simpler esters ofunsaturated acids of 18 to 22 carbon atoms. The present'corns positions,containing the bisphenol type structure chemically bound as an integralpart of a molecule which also contains a'plast'i c'iz'er, maybe reactedwith such reagents The latter product is capable of reduction to asaldehydes ,and epoxides to form compositions which may be polymerized toform valuable insoluble, infusible compositions. However, in the latterproducts, the resinous and plasticizing materials are chemically unitedso that there can be no physical separation thereof during or afterprocessing, and the characteristics contributed by each 'will be foundundiminished in the end product.

Having thus described the invention, a series of illustrative examplesare presented below. These embodiments are not intended to limit theinvention and should not be so construed. Quantities of materialsexpressed are parts by weight unless otherwise indicated.

Example I A mixture of 286 parts of a Diphenolic Acid, prepared fromphenol and levulinic acid, and 268 parts of Mal;- anol 8 (an alcoholprepared by. reduction of soyabean piland having a specified iodinevalue range of 138-154,

produced by Stepan Chemical Company) in a 3-neck Example 1 A mixture of286 parts of a Diphenolic Acid, prepared from phenol and levulinic acid,andv 268 parts of Makanol 9 (an alcohol prepared by reduction of linseedoil and having a specified iodine value range of 193-225, produccdbyStepan Chemical Company). in a 3-neck flask provided with a thermometer,a mechanical agitator, and reflux condenser attached through a watertrap was Example V A mixture of 286 parts of Diphenolic Acid, preparedfrom phenol and levulinic acid, and 268 parts of Adol 37 (2.8% Calcohols, 32.6% C alcohols, 60.7% C alcohols, and 3.9% C alcohols,having an iodine value of 50, produced by Archer-Daniels-MidlandCompany) in a 3-neck flask providedwith a thermometer, a me chanicalagitator, and reflux condenser attached through a water trap wasgraduallyhheatedto 165 C. with continuous agitation; To the moltenmixture was added suflicient xylene to give reflux at the esterificationtem perature. The continuously agitated mixture was heated at 165-l90 C.for 13 hours and held at 195 C. for an additional 30 minutes duringwhich time a water leg vacuum of about 30 mm. pressure was applied toremove the last traces of xylene. This product had an acid value of 7.

Example VI i i Illustrating .how these products may housed in thepreparation of protective coating materials, the product of Example Iwas treated with 3 mols of 37% aqueous gradually heated to 175 C. Asulficient' amount of 7 Example 111 i A mixture of 286 parts ofDiphenolic Acid, prepared from phenol and levulinic acid, and 268 partsof oleyl alcohol in a 3-neck flask provided with a thermometer,

a mechanical agitator, and reflux condenser attached through a watertrap was gradually heated to 175 C.

with continuous agitation. To the molten mixture was added suflicientxylene to give reflux at the esterification temperature. Thecontinuously agitated mixture was heated at 175-190 C, for 10 hours andthen taken to 200 C. for about 1 hour during which time a water legvacuum of about 30 mm. pressure was applied to remove the last traces ofxylene. This product had an acid value of 15. ,1 Example IV formaldehydeusing a trace of HCl as catalyst and heating the mixture for a period of1 hourand 15 minutes at 95 C. with continuous agitation. The water wasremoved by finally heating the product in an open container to atemperature of 110 .C. The resulting product was dissolved in asolventconsisting of. equal parts of butyl acetate, butanol, and methylisobutylketone. Thin films of this product flowed on steel panels andbaked for 15 minutes at 200 C. gave flexible, tack-free surfaces? aWhile there are above disclosed but a limited number of embodiments ofthe'productof the invention herein presented, it is possible'to producestill-other embodime'nts without departing from the inventive conceptherein disclosed, and it is desired, therefore, that only suchlimitations be imposed on the appended claims as are stated therein, orrequired by the prior art.

What is claimed is:

1. As a new' composition of'matter an ester of an unsaturated aliphaticalcohol havingfat least 10 carbon .A mixture of 286 parts of DiphenolicAcid, prepared from phenol and levulinic acid, and 268 parts of Adol 33(8% C alcohols, 84.5% C alcohols, and 7.5% C alcohols, having an iodinevalue of 71, produced by Archer-Daniels-Midland Company) in a 3-neckflask provided with a thermometer, a mechanical agitator, and refluxcondenser attached through a water trap was gradually heated to 175 C.with continuous agitation. To the molten mixture was added suflicientxylene to give reflux at the esterification temperature. 7 Thecontinuously agitated mixture was heated at 175-195 riod of 13 hours andheld at 195 C. for an additional hour 1 during which time a water legvacuum of about 30 mm.

C. for a peatoms and containing only the elements carbon, hydrogen andoxygen and a pentanoic acid having the formula:

C \CHIOHQCOOH wherein X and Y are members of the group consisting ofhydrogen and lower alkyl. 7

2. As a composition of matter the ester of 4,4-bis (4- hydroxyphenyl)pentanoic acid and an unsaturated vegetable oil fatty alcohol.

3. As a composition of matter an ester of 4,4-bis (4- hydrophenyl)pentanoic acid and an unsaturated fish oil fatty alcohol.

4. As a composition of matter the ester of 4,4-bis (4- hydroxyphenyl)pentanoic acid and olcyl alcohol.

5. As a composition of matter theester-of 4,4-bis (4- hydroxyphenyl)pentanoic acid and linseed oil fatty alcohol..

' 6. As a composition of matter the ester of 4,4-bis (4- hydroxyphenyl)pentanoicacid and s oya bean, oil fatty alcohol.

References Cited in the file of this patent.

' lBader: rgAm. Chem. Soc., vol. 76, pp. 4465-5 (1954). Bader:J.-Am.-Chem. Soc., vc1 75, pp. 5416-17 r..;.1 i

UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION Patent No. 2,93352l April 19 1960 Sylvan Owen Greenlee It is hereby certified that errorappears in the printed specification of the above numbered patentrequiring correction and that the said Letters Patent should readascorrected below.

Column 4 line 8,, for "3.9% C read 3,996 C Signed and sealed this 18thday of October 1960.

(SEAL) Attest:

KARL AXLINE ROBERT c. WATSON Attesting Officer Commissioner of Patents

1. AS A NEW COMPOSITION OF MATTER AN ESTER OF AN UNSATURATED ALIPHATICALCOHOL HAVING AT LEAST 10 CARBON ATOMS AND CONTAINING ONLY THE ELEMENTSCARBON, HYDROGEN AND OXYGEN AND A PENTANOIC ACID HAVING THE FORMULA: